The stadium is probably most famous for hosting the 1990 World Cup semi-final between Italy and Argentina. Considered to be the most intriguing match of that World Cup, Diego Maradona asked for the Napoli fans to cheer for Argentina. The Napoli tifosi responded by hanging a flag in their "curva" of the stadium saying "Maradona, Naples loves you, but Italy is our homeland".[1] It was touching for Maradona as Napoli was the only stadium during that World Cup that the Argentinian national anthem was not jeered. The match finished 1–1 after extra time. A penalty shoot out ensued with Maradona fittingly scoring the winning penalty for Argentina.

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Even with Napoli in Serie C1 during the 2005–06 season, Napoli achieved the feat of having the 3rd highest average home attendance in Italy for the season with only two Serie A clubs, Milan and Internazionale having higher attendances. Napoli's final game of the season drew a crowd of 51,000 which now stands as a Serie C record.

San Paolo also hosted Italy's Euro 2008 Qualifier vs Lithuania on 2 September 2006 with the possibility of other qualifiers to be played there in the future.

The Naples city council asked the Italian government for permission to rename the stadium after Diego Maradona. The Argentine legend helped Napoli to win Serie A titles in 1987 and 1990, and he remains a popular figure in the city.

The council voted to ask for the renaming of the San Paolo stadium, but one stumbling block is an Italian law prohibiting public buildings to be named after any person who has not been dead for at least 10 years.